全文获取类型
收费全文 | 5819篇 |
免费 | 196篇 |
国内免费 | 52篇 |
专业分类
化学 | 4361篇 |
晶体学 | 42篇 |
力学 | 217篇 |
综合类 | 2篇 |
数学 | 778篇 |
物理学 | 667篇 |
出版年
2024年 | 11篇 |
2023年 | 61篇 |
2022年 | 308篇 |
2021年 | 307篇 |
2020年 | 207篇 |
2019年 | 230篇 |
2018年 | 218篇 |
2017年 | 168篇 |
2016年 | 292篇 |
2015年 | 202篇 |
2014年 | 210篇 |
2013年 | 533篇 |
2012年 | 359篇 |
2011年 | 383篇 |
2010年 | 237篇 |
2009年 | 204篇 |
2008年 | 258篇 |
2007年 | 259篇 |
2006年 | 207篇 |
2005年 | 181篇 |
2004年 | 164篇 |
2003年 | 140篇 |
2002年 | 144篇 |
2001年 | 54篇 |
2000年 | 63篇 |
1999年 | 44篇 |
1998年 | 30篇 |
1997年 | 44篇 |
1996年 | 40篇 |
1995年 | 32篇 |
1994年 | 39篇 |
1993年 | 31篇 |
1992年 | 32篇 |
1991年 | 28篇 |
1990年 | 43篇 |
1989年 | 26篇 |
1988年 | 22篇 |
1987年 | 26篇 |
1986年 | 27篇 |
1985年 | 32篇 |
1984年 | 19篇 |
1983年 | 17篇 |
1982年 | 25篇 |
1981年 | 20篇 |
1980年 | 14篇 |
1979年 | 16篇 |
1978年 | 11篇 |
1977年 | 12篇 |
1976年 | 9篇 |
1975年 | 6篇 |
排序方式: 共有6067条查询结果,搜索用时 15 毫秒
971.
Mohamed Ben Alaya Thierry Huillet 《Annals of the Institute of Statistical Mathematics》2005,57(4):817-831
With ?(p),p≥0 the Laplace-Stieltjes transform of some infinitely divisible probability distribution, we consider the solutions to the functional equation ?(p-e ?pβΠ i=1 m ?γi (c i p) for somem≥1,c i>0, γ i >0,i=1., …,m, β ε ®. We supply its complete solutions in terms of semistable distributions (the ones obtained whenm=1). We then show how to obtain these solutions as limit laws (r → ∞) of normalized Poisson sums of iid samples when the Poisson intensity λ(r) grows geometrically withr. 相似文献
972.
Equilibrium-based computer models using MINIQUAD-75 program were utilized to determine the stoichiometry and formation constants involved in the systems pyridoxamine(Pm)-glycine (Gly)-imidazole (lmd) with CO(II), Ni(II), Cu(II), Zn(II) and Cd(II) metal ions. The data were obtained from potentiometric pH titration of the various binary and ternary quaternary systems under physiological-like conditions (0.15 M NaNO3-37°C). Various composition ratios of metal and ligands were used. The ligand concentrations did not exceed 4 times the concentration of metal ion in the binary systems and 4 times of the metal ions in ternary systems. In case of the quaternary systems only imidazole concentrations were two or four times the concentrations of metal ions keeping those of other ligands equal to that of metal ions. The stability constants of the quaternary species are discussed in terms of binary and ternary constants as are the effect of ring size on the stability of mixed ligand species. In addition, electrostatic as well as statistical effects also are mentioned and the biological implications of these model equilibria are described. 相似文献
973.
The Madelung constant, the electrostatic and repulsive energies of the compounds MAX, with the PbFCI structure (D74h), are calculated and compared with the experimental cohesive energy. This calculation yields a crude estimate of the Van der Waals energy. The special case of CaHBr is discussed. 相似文献
974.
A simple and accurate spectrophotometric method is described for the determination of epinephrine (EP), norepinephrine (NE) and their bitartrate salts. The method is based on the development of a red colour (lambda(max) 490 nm) with sodium periodate in aqueous alcoholic medium. The colour is stable for at least 1 hr. The molar reacting ratio of EP or NE to periodate is 1:2. The proposed method is particularly suitable for routine analysis of EP and NE injections. The interference due to the sodium metabisulphite normally used as antioxidant can be overcome by addition of acetone. Results for analysis of bulk drugs and injections agree well with those of official methods. 相似文献
975.
Y. Ito Hamdy F. M. Mohamed V. M. Byakov S. V. Stepanov 《Journal of Radioanalytical and Nuclear Chemistry》1996,210(2):607-615
Positronium formation experiments inn-hexane were performed with C2H5Br and CCl4 as inhibitors and others (decalin, tetralin, benzene, naphthalene, phenanthrene) as anti-inhibitors. Although the results can be interpreted in terms of the anti-recombination and anti-inhibition, it is necessary to consider further some new aspects of intra-spur reactions such as shallow tapping of e+ and secondary reactions of Ps. The data thus interpreted correlate excellently with the data of radiation chemistry. 相似文献
976.
Transparent glass-nanocomposite sample [50Li2B4O7-50(SrO-Bi2O3-Nb2O5)] (mol %) was prepared by a conventional melt-quenching technique. Fluorite (Bi3NbO7) and SrBi2Nb2O9 (SBN) was produced by heat-treating the as-prepared sample at 773 K for 6 h (HT773). The nanocrystallites of fluorite and SBN phases in the Li2B4O7 glass matrix were established by differential thermal analysis (DTA) which is confirmed by X-ray powder diffraction (XRD), infrared spectroscopy and transmission electron microscopic (TEM) studies. The influence of heat-treating the as-prepared sample on the optical properties (transmission, optical band gap and Urbach energy) has been investigated. Properties such as dielectric constant and dielectric loss as a function of frequency (120 Hz -100 k Hz) and temperature (300-829 K) are reported. 相似文献
977.
Clark TE Makha M Raston CL Sobolev AN 《Dalton transactions (Cambridge, England : 2003)》2006,(46):5449-5453
p-Bu(t)-calix[5]arene forms crystalline inclusion complexes with o- and m-carboranes in toluene or dichloromethane-hexane, but not with the p-isomer, the extended structures being based on 1 : 1 host-guest supermolecules, with the p-Bu(t)-substituents creating a snug fit for o- and m-carborane; p-carborane forms a highly hexane soluble complex, induced by grinding, which crystallizes as fibres. Solution phase studies showed the presence of a 1 : 1 host-guest stoichiometry with all three isomeric carboranes as determined from Job plots. The association constants for the o- and m-carborane complexes are 6.4 +/- 0.3 M(-1) and 3.8 +/- 0.1 M(-1) respectively, whereas the p-isomer is only weakly associated. Competition experiments involving all three isomers show rapid exchange on the NMR time scale, and no selectivity in solution is evident. Selective association involving the o- and m-isomers in the solid state is therefore remarkable, and it is a manifestation of crystal packing forces which embodies the differences in dipole moments of the carboranes. 相似文献
978.
Bugarcić ZD Nandibewoor ST Hamza MS Heinemann F van Eldik R 《Dalton transactions (Cambridge, England : 2003)》2006,(24):2984-2990
Substitution reactions of the complexes [Pd(bpma)(H2O)]2+, [Pd(bpma)Cl]+, [Pd(dien)(H2O)]2+ and [Pd(dien)Cl]+, where bpma = bis(2-pyridylmethyl)amine and dien = diethylentriamine or 1,5-diamino-3-azapentane, with some nitrogen-donor ligands such as triazole, pyrazole, pyrimidine, pyrazine and pyridazine, were studied in an aqueous 0.10 M NaClO4 at pH 2.8 using variable-temperature and -pressure stopped-flow spectrophotometry. The second-order rate constants indicate that the Pd(II) complexes of bpma, viz. [Pd(bpma)(H2O)]2+ and [Pd(bpma)Cl]+, are more reactive than the complexes of dien, viz. [Pd(dien)(H2O)]2+ and [Pd(dien)Cl]+. Also, the aqua complexes, [Pd(bpma)(H2O)]2+ and [Pd(dien)(H2O)]2+, are much more reactive than the corresponding chloro complexes. The most reactive nucleophile of the five-membered rings is triazole and for the six-membered rings the most reactive one is pyridazine. Activation parameters were determined for all reactions and the negative entropies and volumes of activation (Delta S++, Delta V++) support an associative ligand substitution mechanism. The crystal structure of [Pd(bpma)(H2O)](ClO4)2.2H2O was determined by X-ray diffraction. Crystals are monoclinic with the space group P2(1)/c. The coordination geometry of [Pd(bpma)(H2O)]2+ is distorted square-planar. The Pd-N (central) bond distance, 1.958(5) A, is shorter than the other two Pd-N distances, 2.007(5) and 2.009(5) A. The Pd-O distance is 2.043(5) A. 相似文献
979.
Isab AA Wazeer MI 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,65(1):191-195
Complexation of Ag(+) with captopril, 1-[(2S)-3-mercapto-2-methylpropionyl]-L-proline, has been studied by (1)H and (13)C-NMR spectroscopy. The equilibrium constants for the trans to cis isomers of captopril bound to Ag(+) were measured by (1)H NMR spectroscopy. It is observed that the trans isomer of the drug binds more strongly to Ag(+) between pH 5 and 8, as shown by the broadening of the trans isomer's resonances in (13)C NMR spectra on complexation. A monodentate complexation of the trans captopril with Ag(+) via the thiol site is proposed based on the solid-state NMR and IR data. A superior antimicrobial activity is exhibited by the Cap-Ag(I) complex compared to captopril ligand itself against Heterotrotropic Plate Counts (HPC), Pseudomonas aeruginosa and Fecal streptococcus bacteria. 相似文献
980.
Metal complexes derived from 2,6-pyridinedicarboxaldehydebis(p-hydroxyphenylimine); L1, 2,6-pyridinedicarboxaldehydebis (o-hydroxyphenylimine); L2, are reported and characterized based on elemental analyses, IR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The complexes are found to have the formulae [MX2(L1 or L2)] x nH2O, where M=Fe(II), Co(II), Ni(II), Cu(II) and Zn(II), X=Cl in case of Fe(II), Co(II), Ni(II), Cu(II) complexes and Br in case of Zn(II) complexes and n=0-2.5. The molar conductance data reveal that the chelates are non-electrolytes. IR spectra show that the Schiff bases are coordinated to the metal ions in a terdentate manner with NNN donor sites of the pyridine-N and two azomethine-N. From the magnetic and solid reflectance spectra, it is found that the geometrical structure of these complexes are trigonal bipyramidal (in case of Co(II), Ni(II), Cu(II) and Zn(II) complexes) and octahedral (in case of Fe(II) complexes). The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the coordinated water, anions and ligands (L1 and L2) in the subsequent steps. The activation thermodynamic parameters, such as, E*, DeltaH*, DeltaS* and DeltaG* are calculated from the TG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent organic ligands against one or more bacterial species. 相似文献